Method for finishing polymers



H. H. vlcKERS METHOD FOR FINISHING PoLYMERs May` 6, 1958 2 Sheets-Sheet 1 Filed June 17, 1953 w 0 ouf-mju lnvenfqr Herb erf H Vickers By KM Arrorney May 6, 1958 H. H. vlcKERs METHOD FOR FINISHING PoLYMERs 2 Sheets-Sheet 2 Filed June 17, 1955 503mb@ @z mmmn m25 os r mzoN N mzoN zo 0mm u om l Illlfnlllll. nll.

l Herbert H. Vickers United States Patent O4 METHD FR FINISHFNG POLYMERS Herbert H. Vickers, Union, N. J., assignor to Esso Research and Engineering Company, a corporation of Delaware Application June 17, 1953, Serial No. 362,365

13 Claims. (Ci. Zoll-85.3)

This invention relates to polymerization processes and apparatus and particularly to processes and apparatus 'for the low temperature polymerization of isoolens or mixtures of isoo'lens and other copolymerizable compounds.

It lhas been known for some ltime that high molecular weight polymers, i. e., having a molecular weight of about from l5,000-25,000 up to 300,000 or more (asdetermined by the Staudinger method) are obtained if isoolens, such as isobutylene, are contacted with a Friedel- Crafts type catalyst such as aluminum chloride and the like at temperatures below +14 F. (see, for example, Mueller-Cunradi, U. S. Patent No. 2,203,873, issued June 1l, 1940). More recently it was found that a copolymer which is curable with sulfur is obtained if a mixture of about 70 to 99.5 weight percent of an isoolefin such as isobutylene `with about 30 to 0.5 weight percent of a conjugated diolein having 4 to 5 carbon atoms such as butadiene or isoprene is treated with solution of a Friedel-Crafts type catalyst such asA aluminum chloride in a non-complex forming low freezing solvent such as methyl or ethyl chloride and at temperatures of between -{-l4 F., and 256 F., preferably between 40 F., and 153 F. (see, for example, Australian Patent No. 112,875, issued July 3l, 1941). v Similarly" resins suitable as self-supporting lilms, etc. are prepared by contacting isobutylene and styrene e. g. inthe proportion of 20-80%4 styrene and 80-20% isobutylene, 'at temperatures below 50 C. The polymerizations have been conducted in the presence of either an internal refrigerant such as liqueed ethylene, in which 'case the heat of reaction is removed directly by evaporation of part of the ethylene without the necessity for transferring heat through the surfacesof reaction vessels or through cooling coils arranged in the reaction vessels, or in the presence of yan external refrigerant whereby the heat of reaction is removed by heat exchange through v the wallsy of the reaction vessels. Consequently, the reaction is now carried out in such a manner as to keep the solid polymer particles in a finely divided condition suspended in the cold reaction mixture so that a slurry "ice y However, difficulty has been a suitably dry polymer in this manner. The bed of polymer particles on the dryer conveyor belt tends to flow suiiiciently to forman impermeable mat at the usual dryer temperatures of 225-325 F. before the desired dryness is reached,particularly when low molecular weight poly-mers are vbeing processed. When this occurs the air llow through the dryer is hindered to such an extent that satisfactory dryness of thepolymer is ditticult to procure during normal residence period in the dryer. In addition the mat acts as a lter and picks `np foreign particles from the air. Such particles cause serious faults or holes in any lm subsequently made from the poly` mer. If, on the other hand, an attempt is made to pre-v vent such matting of theV polymer the temperature must be lowered, or the residence time shortened, to a point resulting usually in the incomplete drying 4within the tunnel dryer. in any case, the lmoisture content, porosity, and low temperature of the polymer discharging from the dryer interfere With-theproper operation of the sublsequent milling step which is usually employed to deliver the polymer in a suitable vcondition of dryness and compactness for packaging and sale. For commercial use it is usually required thatpolymers of this type be dried to a moisture content below 0.5%, and it is preferable to reduce this to 0.1 orV 0.2%, or even lower.V

In the Wurth and' Lane patent U. S. y2,472,037, issued May 3l, 1949, Aan atte'mptfwas made to solve the above diiiiculties by the employment of a series of standard screw machines to subject the polymer to a simultaneous dewatering, compacting, and extruding action at an eievated temperature. However, the use of these machines has not proven' satisfactory in actual operation when a large amount of lwater is present and/ or when handling a large volume of polymer. The machines described by f 'It is, therefore, the principal object of this inventionto provide a method of drying polymersrwhich will perof solid polymer particles in the cold reaction mixture is obtained which can be handled at low temperature.

In view of the inflammable nature of certain of the Vrei actants the slurry is discharged into a Well-agitated body of a liquid flashing medium, such as water, in whichl the polymer is suitably insoluble and which is maintained;

at a temperature `well above the boiling point of the majority of the volatile materials accompanying the polymer to form a slurry of finely divided polymer particles in the warm flashing liquid. This slurry is then stripped of any residual volatile materials, the polymer is separated from the vmain body of the liquid, as for examprocessing steps are preferably arranged so that the suc-` n cessive operations are carried out in a continuous i gassingextruder.

zones, the-.rst portion being particularly designed tol mit more complete removal of water from the polymer and more ei'cient operation of any subsequenty milling step.

it is a further object of this-invention to provide means for compacting', dewatering and degassing the polymer with a minimum of air contact in order to prevent its `Contamination with foreign particles.

A still furtherl object of this linvention is to provide means for obtaining a more streamlined, smalle-r, cleaner and cheaperdrying operation than that possible with the usual tunnel driers and their attendant equipment.

These and other objects of this invention are accomplished by continuously subjecting the wet polymer after separating it from the main body of the water to 1the action of a series of specially designedscrew extruders.

The `first of these extruders is a short-barreled compactingextruder having a large feed opening and a tapered screw. The ,second extruderi-s a dewatering and de- This machine is divided into Ytwo dewater and is provided with a rilied barrel. The second portion is provided with a larger screw than the first portion and is separated from the iirst portion by means of a valve and vent arrangement which permits a controlled pressure build-upv in the tirst zone to effectively screen out lthe remaining looserwater. The third extruder in the yseries is similar tothe second except that'v it does not have a rifled barrel and no' drain holes and is designed to increase the polymer temperature to 400 F.,

and `completely dry the product.

, The accompanying drawings illustrate preferred methods for practicing the process of this invention.

encountered in obtaining `flash tanlcas at 8:.in,such.a.manner astoimpinge-a'gainsh 'or even more, `of water per pound of dry polymer may Figli're l1 isy aadiagrammaticrepresentation of a completemnitembodyingthe principlesof this disclosurer Figure 2 is a detailed view incross-section of the extruders of Figure l. a

Referring thereforeto`the drawing;.there'-is"shown^a' 5 reactor 11, wherein'lisoolenic*materials and preferably mixturesK` of` isoolelicffand /diolen'ic materials ('e. g. isoprene or styrene)"a1on`e`or ytoge'therwitha diluent'sup- *l plied throughfeed -inlet-`2` are reacted-*at` low`- temper?MA atures,lpreferably f'around'- @140W F., by the addition1 ofl `1'0 a FxiedelaCra'fts catalystlsupplied'throughlinel The polymer-.forms as"af-slurry of line solid polyrnerparticles'` suspendediincoldre'action medium.eomprisingiunreacted hydrocarbons; diluentsv catalyst` and i catalyst solvenff-as well aslimpurities is withdrawn fromthe reactor *through*l line wand-'gis discharged into lla'sh tank2'5,`c'ontaining a liquid, lsuch .as' water,v inert 'to thek polymer and -m'ainf `tainedata temperatuxehof' aboutfl50f`^F., wherein -the volatlerma-terials 'associated Vwith the polymerare vllasliecl f into vapor:` 'The flashed gases are withdrawn `from-the 20 ashztankfthroughline andlare passed to suitable puri` fcationand recoverymeans for reconditioning the flashedy materialskforreuse inthe process.`

The'water .or otherliquidfashing medium isheated' l as by lthe introduction oijsteam thereinto andvigorously1f25 agitatedxbymeansiof suitable stirrers or therlike to keepl the polymer'suspended as a uniform slurry `inthe flashingl` Y liquidzi :Flashing medium may-also` be withdrawn from the ashwtankthroughdine `7 and `pumpedback into Athe il 80 the polymer 1 streams ienteringrthe 'ash tankitherebyfw` i breaking'ittup in order :to' prevent=agglomeration of the y f riedbarrel 31,-feed opening 33 and screw 34 havmgn polymeninto relatively` large masses r which` mightrplugs. thewaterrslurry'system and which imight contain: excessive :f amounts of trappedvolatileliquid. 35

The polymer is. withdrawn from the ash"tankz.through=\i ff' line 9 as` aY slurryf` iinely divided.solidparticlesiv suspendediinA the warm `flashingl liquid and is Ldischarged into, 1. the stripping, tank10. `:The treatment of the polymer asx a slurry iin the warm'fluid, ifnecessarytwith injection of strippingrvaporsfsu-chfas steam,qis1 carried out to such a degree that nearly all the ,highly ,volatilev materials .,i originally absorbed in or absorbed on theipolymerandw dissolved in,` thefliquidzare removed.; A preferredypefof operation is one in which the volatiles areremovedi-in two 45 zones, the first as in tlash tank at atmospheric or slightly, above atmospheric pressure andftheother as ini/stripping; 1 tankfl atbelow atmospheric'pressure.. PreferablygJ-he water-.nA the.stn'pper 10 is boiling,`.due-toI the use of vacuum. The flow of wateriis c usuallyso large'thatsteam does not haveto befadded-.tothe stripperwhen-the water .v enters hotrenoughn. r y i The slurry oftnely divided' polymer in warm ashing t, liquid, desirably water;y is` passed from the stripping .tauleY 10 `to a decantationzor.iltrationmeans such as, for exam` ple, a vibrating screen wherein it is separated `from;the z-.fr greater part ,of the suspendingliquid. The separated,A polymer which maycarrywith it up to 2 or 3` pounds,

be discharged into a series of dewatering and degassing extruders where the wateris progressively `squeezedout and nally heated under'pressure and dashedv off.

The lrstpiece of equipment in this series is a'tapered' screwVcompacting `extruder^20." Its prime purpose is to Y compact the wet crumb,V squeeze out most of the water,fto less than 10%, andheatfthe polymer :slightlyt'orlOOJ-a 200517".` V'Ihisftapered screw :extruden :becausehof its` u shape; lends` itselfv to `drainage and. .is very` elfectivenr in y squeezingout a large percentage of water. :The taperedfsa design-is `also ofi help in feedingtlre loose crumb, since. the large .end ofithetaperediscrew'is directly.under.,.the 17.0 feed hopper and therefore thasja. feed capacity equal to the largelend of the screw. y

The tapered screw extruder, 20, `isffollowed by'afsingle" screw, dewatering and degassing extruder ""'whvicllA squeezes thewater contentdownto less `tha1'1".5i%"i1" the A"I5 rst zone, adding heat until the polymer temperature is raisedpastithe-boiling'point of water;- At this stage-the extruder pressure is relieved by an increase in barrel diameter, and the vapors are llashed olf through a vent. From the vent to the discharge, the extruder is of normal design and rebuilds the pressure and temperature to extrude the polymer through fthe outlet die at 25o-300 F., while at the same time dashing ot additional vapor and reducingthe water content to less than 2%.

The final Atreatmentis in a single rscrewdegassing extruderl 50 which alsothas one or more-degassing'vents in its middle section. This final extruder builds the polymer temperature up to 30G-450 F., ashing off any remaining vapor, and extrudesa dry polymer inaform for subsequent handling.

Referring now to Figure 2, extruder 20 consists of a tapered body portion 21 having a feed opening 22 in the enlarged end and an extrusion nozzle 23 in the narrow end. i-wThebody'- is fitted'with tapered screw 24 having; ightsZS and operated by prime mover 26. The flights'. are so arrangedithat polymerintroduced through opening 22 is forced toward the extrusion nozzle 23 near` thev dischargediend of the ,feed section 22. The underside of tapered;-:body `portion 21 is providedwith tapered drain 1 hole 2.If. x.TheV particular location of this drain holeper-:Jz'

lmitsa1:slight'tcompacting of the loose polymer toV taken;-

placeabefore it is passed` across the drain opening. A rotarytcutter'z28 operatedsby motor 29 is arranged. adjacentnthenozzle` 23, so `as to cut extruded polymerinto slices. ff

Extruder-30 consists `of a dewatering section 31 andfa; larger dega'ssing sectioni40. f Section 31 is provided withf n ightsp `andoperatecl by prime mover 36. VA water' drain.37isprovided in the forwardend of the section 31.

The degassing section40 is provided with vent opening 41 and screw 42 having flights 43. Screw 42 is a .com .f tinuationnofi screw 33 but is made with'slightly largermA ghts-ithanvscrew 33 to substantially lill the increased spacefinthe larger section 40. Flights-43 are separated t y fromightsi34 by lvalve 44 which is'a thckened'section substantially lfilling the space between the two tlightsA .A 34 and `43 except for a narrow clearance 45 between the block .and the walls of the extruder. An extrusion nozzle 46 isattached to the exit end of degassing section by Y z means-of clamps. l47.

A conveyorf48is provided to convey4 extrudedpolymer.

froml extruden^30 to extruder 50. Extruder 50 is a two `61 is provided-with ights 62, vent 63 and` extrusionf' nozzle 64. ,a

Ihecolznbination` of the three extrudersdescribed` above-,enables-averyfswet polymer to be completely dried lwithoutgathe use of tunnel driers and similar` equipment.

The compaetinglextruder is of particular vimportance in the combinatiornr.v AThe tapered design and thelocation of theutapered;.drain ho1e..make it possible to remove the bnlkwf .therwaterfrom avpolymer water slurry containing` any amount of water.` The location of the 1 drainxhole slightly .forwardofathe feed hopperallows the; polymer-crumb to ybeagglomerated before` it. reaches the hole.-An'y few'particles thatldo pass intothis drainlholeu s do notobstr'f'uct the opening due to itstapered construction t -=1 and ar'elcarried back into the systemiwith the recycled '1 water;-

Actuali operation' with; this extruder has `indicated thatli it willflandle rany amount of water in apolymer-'water 1 slurry', yieldirtg` af compact extruded `polymer which can be fed'intoi any type of dewatering and de'gassing-extrnder` suclras thatdescribed inl the Wurthpatentor preferablyA those described'l above:

Thel advantages of the s inventionJ will-be better undervs stood from a Iconsideration of the following experimental data which are given for the sake of illustration, but without intention of limiting the invention thereto:

' Wet polymer crumb prepared from isoprene and 2.5% isobutylene in accordance with the method described above, +32% moisture, was fed to a 2 twin screw extruder of the type disclosed in the Wurth patent, under varying conditions of temperature and R. P. M. with the following results:

The above data show that free water in the feed hopper is a serious handicap when employing an extruder of the type disclosed in the Wurth patent. The best conditions were obtained with a starved feed which resulted in a lower Water level in the feed hopper and less water to be evaporated in the extruder barrel. .On the other hand the extruder of the present invention under the same conditions handles crumb containing any amount of water. Large quantities of water can be pumped into the feed hopper and be accommodated by the extruder without any effect on the extrusion rate or quality of the polymer.

The nature and objects of the present invention having been thus described and illustrated, what is claimed as new and useful and is desired to be secured by Letters Patent is:

1. In a process for inishing particles of solid polymers containing occluded liquids, the improvement which comprises pressing out suflicient liquid that the polymer particles are compacted, subdividing the compacted agglomerate formed, pressing out suicient liquid from the resulting subdivided material that the liquid content is lessy than about based on polymer, and raising the temperature to a level between about 250 and 450 F. until substantially all of the remaining liquid is volatilized.

2. Process according to claim 1 in which the polymer is a polyisooleiin.

3. Process according to claim 1 in which the polymer is a copolymer of an isooleiin and a multi-olefin.

4. Process according to claim l in which the polymer is a copolymer of an `isooleiin and a vinyl aromatic compound.

5. In a process for nishing solid,4 high molecular Weight polymers prepared by low temperature polymerization of a feed comprising an isooleiin in the presence of a Friedel-Crafts catalyst in which the cold polymer and associated low boiling materials including unreacted monomers and diluents are discharged into a heated liquid medium in which the polymer is insoluble in order to volatilize said associated low boiling materials whereby to form a slurry of polymer particles in the liquid, the improvement which comprises passing the resulting polymer slurry directly to a compacting means tapered into the direction of compaction and having an inlet portion for feed and a discharge portion for product, said compacting means defining a drain aperture located near the discharge portion thereof, said drain aperture being tapered from inside outwardly to prevent plugging, passing the polymer through said compacting means, and subdividing the resulting compacted agglomerate formed.

6. In a process for finishing a solid high molecular weight rubbery polymer prepared by Friedel-Crafts catalytic low temperature polymerization in which the cold polymer and'lower boiling unreacted monomers -and diluents are discharged into a liquid medium heated to a temperature suilicient to flash off substantially all of said lower boiling materials whereby to form a slurry of polymer particles in the liquid, the improvement which comprises passing the resulting polymer slurry through an extrusion zone tapered in the direction of extrusion and maintained at a temperature between about and 200 F., cutting the extruded polymer formed into segments, passing said polymer segments through a twostage deliquefying and degassing screw extrusion zone, the deliquefying portion being maintained at a temperature above about 212 F. and reducing the liquid content of the polymer to less than about 5%, the degassing portion being maintained at a temperature between about 250 and 300 F. and reducing the liquid content of the polymer to less than about 2%, and then substantially completely drying the polymer at a temperature between about 300 and 450 F.

7. In a process for nishing solid, high molecular weight rubbery polymers prepared from a feed comprising at least one isoolen at low temperatures in the presence of a Friedel-Crafts catalyst, in which process the cold polymer product and associated low boiling materials including unreacted monomers and diluents are discharged into hot Water in which the polymer is insoluble in order to flash off said associated low boiling -materials whereby to form -a slurry of polymer particles in water, the improvement which comprises separating wet polymer particles from the water, subjecting the separated wet polymer particles to screw extrusion through an extrusion zone tapered into the direction of extrusion and maintained at a temperature between about 100 and 200 F. whereby the polymer is freed of about 90% of residual water and compacted, successively cutting the extruded polymer formed into segments, passing said 'polymer segments through a two-stage extrusion zone maintained in the lirst stage at a temperature above about 212 F. whereby the polymer is dewatered so as to contain less than about 5% Water, said second stage being maintained at a temperature between about 250 and 300 F. whereby the polymer is degassed of about an additional 3% water, and then passing the polymer through an extrusion zone maintained at a temperature between about 300 and 450 F. whereby the polymer is essentially freed of substantially all residual Water and is further degassed and compacted.

8. Process according to claim 7 in which the iso-olefin is isobutylene.

9. Process according to claim 7 in which the isobutylene is copolymerized with 30 to 0.5 wt. percent of a conjugated diolefn having 4 to 5 carbon atoms.

10. Process according to claim 9 in which the diolen is isoprene.

1l. Process laccording to claim 7 in which the isobutylene is copolymen'zed with 20 to 80 wt. percent of styrene.

l2. In an apparatus for treating solids and liquids, the combination which comprises a conical shaped compacting screw extruder tapered in the direction of compaction, said extruder having a large inlet portion and a small discharge portion, the lower surface of said extruder defining a drain aperture for liquid located near the discharge portion of said extruder, said drain aperture being tapered from the inside outwardly to prevent plugging, means for introducing a solid material into the inlet portion of said extruder, and a cutting means cooperable with said discharge portion, said cutting means being adapted to successively cut the extruded solid formed into segments.

13. In an apparatus for nshing polymers containing vaporizable liquids, the combination which comprises a hollow two-stage dewatering and degassing screw extruder, having an inlet portion and a discharge portion, said extruder comprising a cylindrical housing member di- 7 videdintoairst andia secondisectonzarrotatableltapered screw` member extending intoreach. of said sections, .'the first; sectionebeingfofwsmaller.:diameter. :than l the -second section land .fdeningf a lower. drainy aperture 2 adapted to dischargesliquid itherefrom," the: second section .communicating-withihe rst section and being a degassing section deningeavent for-removingvapors formed,said vent beingflocated in an klipper., portionfof said second asection.

r-References litedvinhefile of thispatent -flUNITEDSTATES APATENTS 

1. IN A PROCESS FOR FINISHING PARTICLES OF SOLID POLYMERS CONTAINING OCCLUDED LIQUIDS, THE IMPROVEMENT WHICH COMPRISES PRESSING OUT SUFFICIENT LIQUID THAT THE POLYMER PARTICLES ARE COMPACTED, SUBDIVIDING THE COMPACTED AGGLOMERATE FORMED, PRESSING OUT SUFFICIENT LIQUID FROM THE RESULTING SUBDIVIDED MATERIAL THAT THE LIQUID CONTENT IS LESS THAN ABOUT 5% BASED ON POLYMER, AND RAISING THE TEMPERATURE TO A LEVEL BETWEEN ABOUT 250* AND 450*F. 